The interaction of gaseous CO 2 with the surface of amine-modified nanoporous clays has been studied. CO 2 adsorption and adsorption microcalorimetry revealed high adsorption capacity and strong interaction with the surface at low pressures, due to the presence of amine groups. Considerable surface heterogeneity and high initial adsorption heat (125 kJ mol -1 ) have been observed, although the adsorption was reversible with hysteresis at low pressures and very slow desorption kinetics. Interaction between 13 CO 2 and the surface of the nanoporous clay materials has been investigated by 13 C and 15 N magic-angle spinning (MAS) NMR. 13 C NMR resonances at ca. 164 and 160 ppm have been assigned to, respectively, carbamate and carbamic acid, and the stability of these species have been studied. Peak areas and the amount of 13 CO 2 adsorbed allowed the determination of the concentration of carbamate and carbamic acid. To the best of our knowledge, this is the first time that solid-state NMR is used to clearly establish the formation of amine-CO 2 bonding at the surface of amine-modified nanoporous materials and to identify the nature of the species formed. The results presented here shed light on the mechanism of CO 2 activation, since the CO 2 adsorption on the surface of such materials is the activation step that allows further reactions to occur. The instability of the carbamate and carbamic acid species formed on the surface is important in explaining the reactivity of these intermediates and supports the possible application of these materials in CO 2 activation.
Two-dimensional (2D) solid-state nuclear magnetic resonance (SSNMR) experiments on samples loaded with C-labeled CO, "under controlled partial pressures", have been performed in this work, revealing unprecedented structural details about the formation of CO adducts from its reaction with various amine-functionalized SBA-15 containing amines having distinct steric hindrances (e.g., primary, secondary) and similar loadings. Three chemisorbed CO species were identified by NMR from distinct carbonyl environments resonating at δ ≈ 153, 160, and 164 ppm. The newly reported chemisorbed CO species at δ ≈ 153 ppm was found to be extremely moisture dependent. A comprehensive H-based SSNMR study [1DH and 2D H-X heteronuclear correlation (HETCOR, X =C, Si) experiments] was performed on samples subjected to different treatments. It was found that all chemisorbed CO species are involved in hydrogen bonds (HBs) with either surface silanols or neighboring alkylamines. H chemical shifts up to 11.8 ppm revealed that certain chemisorbed CO species are engaged in very strong HBs. We effectively demonstrate that NMR may help in discriminating among free and hydrogen-bonded functional groups. C{N} dipolar-recoupling NMR showed that the formation of carbonate or bicarbonate is excluded. Density functional theory calculations on models of alkylamines grafted into the silica surface assisted the H/C assignments and validated various HB arrangements that may occur upon formation of carbamic acid. This work extends the understanding of the chemisorbed CO structures that are formed upon bonding of CO with surface amines and readily released from the surface by pressure swing.
The separation of ethylene from ethane is one of the most energy-intensive single distillations practiced. This separation could be alternatively made by an adsorption process if the adsorbent would preferentially adsorb ethane over ethylene. Materials that exhibit this feature are scarce. Here, we report the case of a metal-organic framework, the IRMOF-8, for which the adsorption isotherms of ethane and ethylene were measured at 298 and 318 K up to pressures of 1000 kPa. Separation of ethane/ethylene mixtures was achieved in flow experiments using a IRMOF-8 filled column. The interaction of gas molecules with the surface of IRMOF-8 was explored using density functional theory (DFT) methods. We show both experimentally and computationally that, as a result of the difference in the interaction energies of ethane and ethylene in IRMOF-8, this material presents the preferential adsorption of ethane over ethylene. The results obtained in this study suggest that MOFs with ligands exhibiting high aromaticity character are prone to adsorb ethane preferably over ethylene.
Grand canonical Monte Carlo simulations were used to explore the adsorption behavior of methane, ethane, ethylene, and carbon dioxide in isoreticular metal-organic frameworks, IRMOF-1, noninterpenetrated IRMOF-8, and interpenetrated IRMOF-8. The simulated isotherms are compared with experimentally measured isotherms, when available, and a good agreement is observed. In the case of IRMOF-8, the agreement is much better for the interpenetrated model than for the noninterpenetrated model, suggesting that the experimental data was obtained on an essentially interpenetrated structure. Simulations show that carbon dioxide is preferentially adsorbed over methane, and a selective adsorption at low pressures of ethane over ethylene, especially in the case of IRMOF-8, confirm recent experimental results. Analysis of simulation results on both the interpenetrated and the noninterpenetrated structures shows that interpenetration is responsible for the higher adsorbed amounts of ethane at low pressures (<100 kPa) and for the interesting selectivity for ethane in ethane/ethylene binary mixtures. Van der Waals interactions seem to be enhanced in the interpenetrated structure, favoring ethane adsorption. This indicates that interpenetrated MOF structures may be of interest for the separation of small gas molecules.
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